Esters of alpha-halogen carboxy acids with oxyalkylated phenolaldehyde resins



Patented Jan. 8, 1952 ESTERS F ALPHA-HALOGEN CARBOXY ACIDS WITH OXYALKYLATED PHENOL- ALDEHYDE RESINS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 13, 1948,

Serial No. 65,081

8 Claims. (01. 26053) The present invention is concerned with certain new chemical products, compounds, or compositions which have useful application in various arts. This invention is a continuation-inpart of our copending application Serial No. 726,205, filed February 3, 1947, and now abandoned. It includes methods or procedures for manufacturing said new chemical products, compounds, or compositions, as well as the products, compounds, or compositions themselves. Said new compositions are esters of an alpha-halogen monocarboxylic acid having not over 6 carbon atoms and hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) An alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive towards said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2, 4, 6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (RiOM, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This specific application is described and claimed in our copending application, Serial No. 65,080, filed December 13, 1948, and now Patent 2,542,000, granted February 20, 1951. The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and Spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles such as sewage, coal Washing waste Water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

The oxyalkylated resins, used to provide the alcoholic radical of the new esters, are described in our Patents 2,499,370, granted March 7, 1950. and 2,542,000, granted February 20, 1951, and reference is made to those patents for a description of the phenol-aldehyde resins used to produce the alcoholic products. For specific examples of the resins, reference is made to Examples 111 through 103a of Patent 2,499,370. For examples of oxyalkylated products derived from these resins reference is made to the tables in columns 31 through 46 of Patent 2,542,000.

The herein contemplated total or partial esters are derived from alpha halogen monocarboxylic acids having not over 6 carbon atoms. Typical acids exemplifying this class are chloroacetic, dichloroacetic, bromoacetic, alpha bromobutyric, etc. Needless to say that our preference is to employ either the acids themselves or the acyl chlorides.

It is our preference to use chloroacetic acid for the reason that it is cheap and particularly reactive. Chloroacetyl chloride is a preferred reactant from the standpoint of reactivity but is objectionable for two reasons, one being that in eliminating hydrochloric acid in the reaction there is a, tendency to cause corrosion of the apparatus, unless especially designed, and secondly, this reactant is comparatively expensive. However, except for these two objections it may be considered as a preferred reactant. Our preference is to use any alpha-halogen carboxylic acid of not over 6 carbon atoms. Other suitable acids include alpha-chloropropionic acid, alpha-chlorobutyric acid, alpha-bromoisocaproic acid, bromoacetic acid, iodoacetic acid, etc. The acyl halides of these acids, of course, may be employed.

In many instances the alpha-halogenated acylchloride is as readily available as the alpha-halogen acid. The reason for this is the fact that it is diliicult to halogenate an acid so as to introduce the halogen in an alpha position, but an acyl halide reacts more rapidly and the halogen enters the alpha position due to the negative efiect of both the chlorine atom and the carbonyl atom. Under such circumstances where the alpha-chloroacyl acid is available there is no reason, of course, to hydrolyze an acyl chloride to the acid in order to use the acid instead.

Example The method employed, whether on a large scale or a laboratory scale, is susceptible to use in connection with resins oi the kind described where all, or substantially all, the phenolic hydroxyls have been changed into alkanol hydroxyl radicals or have been oxyalkylated further. In other words, such procedure is perfectly satisfactory for a compound. obtained by treating a resin of the kind described under the heading of Example 1a, et seq., with ethylene oxide or the like, on an equimolar ratio based on each phenolic hydroxyl present. In most of the examples, and particularly since such examples exemplify reagents herein employed, more than one mole of ethylene oxide has been introduced per phenolic hydroxyl. See Examples 1%) et seq. of Patent 2,499,370.

We prefer to use a glass resin pot oi the kind decribed under the heading of Example 1a of Patent 2,499,370. Such resin pot may vary in size, for instance, so as to have a capacity varying from 500 to 1500 00., with 1000 or 1250 00., most convenient. The upper part of the apparatus is the same as previously described, to Wit, it includes a stirring device, a thermometer well, a separatory funnel or other means of adding reactants, and a water-cooled reflux condenser equipped with a phase-separating device so that water of reaction or condensation can be removed. The resin pot is heated, as before, with a glass fiber electric heater. The reaction can be conducted with or without the use of a catalyst such as para-toluene sulfonic acid. We prefer to use such a catalyst. The reaction is generally complete within 4 to 6 hours and the completeness of reaction can be judged by the disappearance of the carboxyl acid value, or by the reduction of hydroxyl value in the acid mass, or by measuring the water of reaction obtained in the condenser trap. Such value, however, is apt to run in excess of, theoretical.

All reactants employed, such as chloroacetic acid or para-toluene sulfonic acid, were of technical grade. The xylene employed as a solvent was of the technical grade.

Grams Xylene-containing oxyalkylated resin 10412 of Patent 2,542,000 800 Chloroacetic acid 198 Xylene 534 Para-toluene sulfonic acid 53 The above ratios are equimolar. The mixture was heated with stirring under reflux for 6 hours at a temperature of 145 C., during which time 35 cc. of water were collected in the phase-separating trap, the xylene being returned to the reaction mixture. This water was in excess of theoretical. A small portion of this product was poured in a thin film on a glass plate and allowed to stand at room temperature for several days so as to insure evaporation of the xylene. Examination of the solvent-free product showed it Example 20 The apparatus described in Example 1c was charged with,

Grams Xylene-containing oxyalkylated resin 1051) of Patent 2,542,000 600 Chloroacetic acid 85.6 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period or about 6.5 hours at a temperature of 142 0., during which time 22.4 grams of water were collected. The product, after removal of solvent, was an amber, tacky, semi-solid, slightly soluble in water, with some foaming.

Example 30 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 10Gb of Patent 2,542,000 600 Chloroacetic acid 73.0 Xylene 400 Para-toluene sulfonic acid 40 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 1071) of Patent 2,542,000 600 Chloroacetic acid 56.8 Xylene 400 Para-toluene sulfonic acid- 40 The mixture was heated at reflux with stirring over a. period of about 5.5 hours, at a temperature of 142 0., during which time 11.4 grams of water were collected. The product, after removal of solvent, was a clear, yellow-brown syrup, well soluble in water, with considerable foaming.

Example 50 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 10811 of Patent 2,542,000 600 Chloroacetic acid c 46.8 Xylene 400 Para-toluene sulfonic acid 40 Thamixturewasheated atreflux with stirring over a period of about 6 hours at a temperature of C., during which time 11.2 grams of water were collected. The product, after removal of solvent, was a clear, yellow-brown sticky syrup, very soluble in water, with heavy foaming.

Example 60 The apparatus described in Example was charged with Grams Xylene-containing oxyalkylated resin 10% of Patent 2,542,000 600 Chloroacetic acid 152 Xylene 400 Para-toluene sulfonic acid 40 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 11% of Patent 2,542,000 600 Chloroacetic acid 111.7 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 5 hours, at a temperature of 142 C., during which time 26 grams of water were collected. The product, after removal of solvent, was a yellow, sticky, viscous liquid, slightly soluble in water, with some foaming.

Example 80 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 11112 of Patent 2,542,000 600 Chloroacetic acid 62.4 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about '7 hours at a temperature of 141 C., during which time 15.2 grams of water were collected. The product, after removal of solvent, was a brown, sticky, semi-fluid mass, slightly soluble in water, with little foaming.

Example 90 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 112b of Patent 2,542,000 600 Chloroacetic acid 50.0 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 7 hours, at a temperature of 142 C., during which time 11.0 grams of water were collected. The product, after removal of solvent, was an amber, sticky, semi-fluid mass, slightly soluble in water, with a fair amount of learning.

' 6 Eramp'le The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 113b of Patent 2,542,000 600 Chloroacetic acid 39.6 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 5.5 hours at a temperature of 137 C., during which time 29 grams of water were collected. The product, after removal of solvent, was a brown, sticky syrup, fairly soluble in water with considerable foaming.

Example .The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 11411 of Patent 2,542,000 600 Chloroacetic acid 163.5 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 5 hours at a temperature of 143 C., during which time 39 grams of water were collected. The product, after removal of solvent, was a thick, amber syrup, little solu-. ble in water with little foaming.

Example 12c The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 11512 of Patent 2,542,000 600 Chloroacetic acid 71.4 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6.5 hours at a temperature of 144 C., during which time 17.8 grams of water were collected. The product, after removal of solvent, was a viscous, yellow syrup, somewhat soluble in water with some foaming.

Example 13c The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 116b of'lPatent 2,542,000 600 Chloroacetic acid 60.2 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6.5 hours, at a temperature of 144 C., during which time 11.8 grams of water were collected. The product, after removal of solvent, was a yellowish, thicld, sticky syrup, fairly soluble in water with a fair amount of foaming. Example The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 1171) of Patent 2,542,000 600 Chloroacetic acid 49.8 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a periodof about 4.5 hours at a temperature of 144 C., during which time 8 gramsof water were. collected. The product, after removal of solvent, was a clear, light brown, semi-fluid syrup, wellsoluble in water with good foaming;

Example 16c The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 1195 of Patent 2,542,000- 600 Chloroacetic acid 153* Xylene 4'00 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about hours at a temperature (if-144 C., during which time 36.4 grams of water were collected. The product, after removal of solvent, was an amber, viscous, semi-solid little soluble inwater with little foaming.

Example 17c The apparatus described in Example was charged with Grams Xylene-containing oxyalkylated resin 120?) of Patent 2,542,000 600 Chloroacetic acid 113.5 Xylene 400 Para-toluene sulfonic acid The mixture was heated at reflux with stirring over a period of about 6 hours at a temperature of 143% C., during which time 27' grams of water were collected. The product, after removal of solvent, was a yellow, thick, semi-solid, little soluble in water" with little foaming;

Earample 18c Theapparatus described in. Example 10 was charged with Grams Xylene-containing oxyalkylated resin 1211:

of Patent 2,542,000 r 600. Chloroacetic acid 62.8 Xylene 400 Para-toluene s'ulfomc acid 40 The mixture was heated at reflux with stirring over a period of about 4 hours at a-t'em perature of 141 C., during which time 13 grams of water were collected. The product, aftei"r'e-' moval of solvent, was a viscous, amber fluid, somewhat soluble in water with some foaming;

Example The apparatus described in Example 1c was charged with Grams Xylene-containing oxyalkylated resin 122?) of Patent 2,542,000 600 Chloroacetic acid 51.2 Xylene 400 Para-toluene sulfonic acid 40' The. mixture was heated at reflux with stirring over a period of about 6.5 hours at atam perature of 143 C.,. during which time 10.2 grams" of Water were collected. The product, after removalof solvent, was a yellowish, viscous liquid, fairly soluble in water with some foaming.

Example 200 The apparatus described in Example 10 was charged with I Grams Xylene-containing oxyalkylated resin 123D of Patent 2,542,000 600 Chloroacetic acid 42.4 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated atrefiux with stirring over a period of about 6 hours at a temperature of 143 0;, during which time 12.2 grams of water were collected. The product, after removal of solvent, was an amber semi-solid, fairly soluble in water with some foaming.

Example 210 The apparatus described in Example 1c was charged with Grams Xylene-containing oxyalkylated resin 124?) of Patent 2,542,000 600 Chloroacetic acid 205 Xylene 400 Para-toluene sulfonic acid a 40 The mixture was heated at reflux with stirring over a period of about 5 hours at a temperature of 142 C., during which time 49 grams of water were collected. The product, after removal of solvent, was a yellowish semi-fluid, little soluble in water with little foaming.

Example 22c The apparatus described in Example 1c was charged with I Grams I Xylene-containing oxy'alkylated resin 1251) of Patent 2,542,000 600 Chloroacetic acid 147.5 Xylene 400 Para -toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6 hours at a'temperature of 144 C., during which time 35.1 grams of water were collected. The product, after removal of solvent, was an amber, viscous liquid, slightly soluble in water with little foaming.

Example 230 The apparatus described in Example 10 was charged with 9 The mixture was heated at reflux with stirring over a period of about 6 hours at a temperature of 140 C., during which time 16 grams of water were collected. The'product, after removal of solvent,-was a turbid brown, sticky syrup, somewhat soluble in water with a fair amount of foaming.

Example 240 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 1271) of Patent 2,542,000 600 Chloroacetic acid 39.6 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about hours at a temperature of 144 C., during which time 16 grams of water were collected. The product, after removal of solvent was a clear, brown, sticky syrup, very soluble in water with much foaming.

Example 250 The apparatus described' in Example was charged with Grams Xylene-containing oxyalkylated resin 12% of Patent 2,542,000 600 Chloroacetic acid 47.2 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6 hours at a temperature of 143 C., during which time 16.2 grams of water were collected. The product, after removal of solvent, was a dark brown, thick, sticky syrup, very soluble in water, with much foaming.

Example 260 The apparatus described in Example 10 was charged with Grams Xylene-contaimng oxyalkylated resin 12917 of Patent 2,542,000 600 Chloroacetic acid 145.8 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6 hours at a temperature of 143 C., during which time 34.5 grams of water were collected. The product, after removal of solvent, was a yellow-brown semi-solid, little soluble in Water with little foaming.

The mixture was heated at reflux with stirring over a period of about 5 hours at a temperature of 142 C., during which time 26 grams of water were collected. The product, after removal of solvent, was a, viscous yellow-brown fluid, slightly soluble in water with little foaming.

\ Example 280 I The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 131b of Patent 2,542,000 600 Chloroacetic acid 66.2 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 4 hours at a temperature of 145 C., during which time 8.6 grams of water were collected. The product, after removal of solvent, was a yellowish semi-solid, fairly soluble in water with some foaming.

Example 29c The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 13212 of Patent 2,542,000 600 Chloroacetic acid 50.0 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 5.5 hours at a temperature of 142 C., during which time 10.4 grams of water were collected. The product, after removal of solvent, was a viscous yellow fluid, fairly soluble in water with some foaming.

Example 300 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 13% of Patent 2,542,000 600 Chloroacetic acid 41.6 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 2.5 hours at a temperature of 154 C., during which time 5.6 grams of water were collected. The product, after removal. of solvent, was an amber semi-fluid, quite soluble in water with considerable foaming.

Example 310 The apparatus described in Example 10 was charged with v Grams Xylene-containing oxyalkylated resin 135b of Patent 2,542,000 611 Chloroacetic acid 94.5 Xylene 400 Para-toluene sulfonic acid 40 The mixture was heated at reflux with stirring over a period of about 6 hours at a temperature of 141 C., during which time 20.6 grams of water were collected. The product, after removal of solvent, was a yellowish viscous liquid, slightly soluble in water with some foaming.

Example 320 The apparatus described in Example 10 was charged with Grams Xylene-containing oxyalkylated resin 13% of Patent 2,542,000 790 Chloroacetic acid 70.9 Xylene 400 Para-toluene sulfonic acid 40 acsnasa 111 The mixture washeated at reflux with stirring over a. period 01 about 6 hours at a temperature of 144 0., during which time 2010 grams of water were collected. The product, after removal of solvent. was an amber, thick fluid, fairly soluble in water with considerable foaming;

Example 33c- The apparatus described in Example 10 was charged with.

Grams Xylene-containing oxyalkylated resin 139bof Patent.2,542.,000 720 Chloroacetic. acid: 118.2 Xylene r d80.6

Example 340 The apparatus described: in- Example: 10. was charged with Grams Xylene-containing oxyalky-lated resini 1401) of Patent 2,542,000 7.20 Chloroacetic acid 90 Xylene 480.6 Para-toluene sulfonicacid 48.1

The mixture was heated at reflux with stirringover. a period of about 8.5 hours at a temperature of 140 C., during; which time. 16 grams'of water were. collected. The product,- after removal of solvent, was a yellow-brown, viscous liquid.somewhat. soluble in water with some foaming.

Example c The apparatus described. in. Example 1c. was.

Para-toluene. sulfonic acid. l. 481

The. mixture was heated at reflux with stirring over a period of about fi-hours abatemperature.

of 141C; during which time. 1615: grams oiwater were collected; The product, after removal of solvent, was an amber, sticky semi-fluid, fairlysoluble in water with some foaming.

Example. 360

The apparatus described in- Example 10 was charged with Grams Xylene-containing oxyalkylatedresin 14212 of Patent 2,5425000 720' Chloroacetic acid 57.5 Xylene 480.6 Para-toluene. sulfionic acid 48.1

Themixture was heated at reflux with stirring over a period of. about 6 hours at a temperature of lei-4 (3., during which time ldg-ramsof water were collected. The product, after removal of solvent, was a brownish amber semi-liquid, well.

soluble in water with considerable. foaming.

12 Example 37a The apparatus described in- Examplelc was charged with Grams Xylene-containing oxyalkyl'ated' resin 143D oiP'a-t'ent 2,542,000 720- Chloroacetic acid 48.6 Xylene 480.6 Para-toluene. sulfonic. acid 48.1

The mixture was heated at reflux with stirring overa period of about 6 hours at a temperature of 141 C., during: Which time 11 grams: of water were collected... The. product, after removal of solvent,.was.a.yellowish semi-fluid',.very. solubl'edrr water with. considerable foaming.

Example 380 The apparatus described in Example 10 was charged with Grams Xylene containing oxyalkylated resin 14Gb ofPatent 2,542,000 754.6 Chl'oroacetic acid 75.6' Xylene 160 Para-toluene sulfonic acid 32 The mixture was heated at reflux with stirring. over aperiod of about 6 hours at a temperature of158" C.,- during which time 15- gramsof. waterwere collected. The product, after removal of solvent, was an amber, sticky, semiefluid. mass. somewhat soluble in water with some foaming.

Example 390 The apparatus described in Example 10' was charged with Grams Xylene-containing oxyalkylat'ed resin I47b of Patent 2,542,000 638' Chloroacetic acid 5119- Xylene 220 Para-toluene sulfonic acid 27.5

The mixture was heated at reflux with stirring. over av period of about 6 hours at a temperature of 145 C.,. during whichtime 9.5 grams of water. were collected. The product, after removal. of solvent, was a brownish-yellow, sticky syrup, quitesolublein water with fair foaming.

Attention is directed to" the. following, fact: Theoxyalkylatedresins herein used as intermediate materials. for further reaction to provide more complex derivatives are characterisedby' having certain minimum hydrophile properties; as de:-- scribed, and it is. particularly desirablethat these: hydrophil'e properties be sufficient to produce. an. emulsion when mixed with xylene'in themannerpreviously described.

Needless to say, when. a derivative is formed, such derivative may have somewhat altered hydrophilecharacter, onstated another way; may have an altered hydrophobe-hydrophilebalance. If an ester is prepared from a high molal acid, hydrophile character is increased. If such: ester is prepared from sulfo-benzoic acid. or the like, the hydrophile character may be enhanced. This is also true in even more complicated derivatives, such as the introduction of a; quaternary nitro'-' gen atom radical. In ,the formation of esters, the hydrophobe-hydrophilebalancee is eiie'cte'd; by

the. factor of: whether one preparea complete. or

partial ester. In a generalv way, although the herein described compounds are valuable: forvari-' ous purposes, particularly demulsification, even. though the hydrophobecharacter may be. in:-

resins, and when such derivatives also show at least such minimum hydrophile character, they are unquestionably most advantageous, particularly for use as demulsifiers. Thus, in the hereto appended claims, in pointing out the invention in such specific character, at least part of the claims are directed to the derivatives in which the derivative meets the same final test in regard to the production of a xylene emulsion. Stated another way, the final derivative must be at least as hydrophile, or more so, than the minimum requirement for the oxyalkylated resin, as defined.

Having thus described our inventiomwhat we claim and desire to secure by Letters Patent is:

1. An ester in which the acyl radical is that of an alpha-halogen monocarboxylic acid having not over 6 carbon atoms and composed of carbon, hydrogen, oxygen and halogen and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible. organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive towards said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 2 carbon atoms and substituted in .one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (R) n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus.

2. A choloroacetate of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglyclde, and (B) an oxyalkylation susceptible, fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive towards said phenol; said resin being formed in the substantial absence of phenols of functionality 14 greater than two; said mula:

in which a is a hydrocarbon radicaljhaving at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin'being characterized by the introduction into the resin molecule varying from 1-to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso.

that the hydrophile propertiesof the ester. as well as the oxyalkylated resin in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

3. A chloroacetate of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive towards said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)11-; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ester as Well as the oxyethylated resin in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

4. A chloroacetate of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionphenol beingof the for-= aiitygreater, than two; said. phenol being rofz the: formula wherein 10 is a; numeral varying from 1 to-2 0; with the'proviso that at' -least 2 moles of-ethyl'ene oxide" be introducedforeach phenolic nucleus;- and with the" final proviso that'the hydrophile properties-of the ester as well as the oxyalkyiated resin in an equal weight of xylene are-sufficienttoproduce anemulsion when said xylene solution is shaken. vigorously with one. tov three.--,vele.; umes of water.

5. The product of claim 4, wherein Reissubn. stituted'in the para position.

6; The product of claim wherein B; 15-21. butyi: radical substituted in the para, position.

7:. The product of claim. 4, wherein R1. is: an: amylradical substituted in the parapositiom 8". Thezproduct of claim 4, whereinR is a nonylz "101 radical substituted in the para position.

MELVIN DE GROOTE: BERNHARD KEISER.

REFERENCES CITED The, following references are of record the file of this patent:

UNITED STATES PA'IENTS.

Number Name Date 291 2,169,991 Rosenbium ---,-V-- .Aug. 15 loss 2,2 Krumbhaar J 6, 1.94.2. 5 5 ock et NQY- 23; $25 2,499,365 De Groote MarJL 195,11. 

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF AN ALPHA-HALOGEN MONOCARBOXYLIC ACID HAVING NOT OVER 6 CARBON ATOMS AND COMPOSED OF CARBON, HYDROGEN, OXYGEN AND HALOGEN AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARDS SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 